Thiolated gold nanoparticle solvation in near-critical fluids: The role of density, temperature, and topology

We employ molecular dynamics simulations to study the structure and solvation thermodynamics of thiolated gold nanoparticles of size 1.2 and 1.6 nm with ligand of chain length 8–16 carbons in ethane and propane over a wide range of densities close to the critical isotherm. The Helmholtz free energy is estimated by explicitly calculating the change in entropy and internal energy of solvation, and the effect of density and temperature on fluctuation-driven inherent anisotropy in the ligand corona is characterized. Since the topological variation further accentuates this instantaneous asymmetry in the ligand cloud, the anisotropy with varying surface coverage and chain length is also studied including the solvent contributions to the entropic and energetic metrics. Our results are consistent with the experiment, suggesting a route of obtaining structural insights into solvation thermodynamics that could be useful for understanding the stability of nanoparticle dispersions.